CN105964659B - A kind of aluminum cell waste cathode carbon block comprehensive recovering process - Google Patents
A kind of aluminum cell waste cathode carbon block comprehensive recovering process Download PDFInfo
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- CN105964659B CN105964659B CN201610364167.5A CN201610364167A CN105964659B CN 105964659 B CN105964659 B CN 105964659B CN 201610364167 A CN201610364167 A CN 201610364167A CN 105964659 B CN105964659 B CN 105964659B
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- 239000002699 waste material Substances 0.000 title claims abstract description 101
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 77
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 62
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000000843 powder Substances 0.000 claims abstract description 42
- 239000003792 electrolyte Substances 0.000 claims abstract description 40
- 239000003513 alkali Substances 0.000 claims abstract description 32
- 239000013078 crystal Substances 0.000 claims abstract description 29
- 239000000706 filtrate Substances 0.000 claims abstract description 28
- 239000002893 slag Substances 0.000 claims abstract description 26
- 239000007787 solid Substances 0.000 claims abstract description 26
- 238000002425 crystallisation Methods 0.000 claims abstract description 25
- 230000008025 crystallization Effects 0.000 claims abstract description 25
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 20
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims abstract description 19
- 238000001914 filtration Methods 0.000 claims abstract description 18
- 238000005188 flotation Methods 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 14
- 238000009413 insulation Methods 0.000 claims abstract description 8
- 238000002386 leaching Methods 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 37
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 239000004088 foaming agent Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 10
- 239000003350 kerosene Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 235000019353 potassium silicate Nutrition 0.000 claims description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 8
- 239000003610 charcoal Substances 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 claims description 4
- 239000002283 diesel fuel Substances 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 17
- 239000002910 solid waste Substances 0.000 abstract description 3
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 235000010210 aluminium Nutrition 0.000 description 49
- 238000001035 drying Methods 0.000 description 18
- 229910052573 porcelain Inorganic materials 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 13
- 239000004411 aluminium Substances 0.000 description 10
- 238000000926 separation method Methods 0.000 description 9
- 238000005868 electrolysis reaction Methods 0.000 description 7
- 238000011049 filling Methods 0.000 description 7
- 230000000881 depressing effect Effects 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- -1 hydrogen Aluminum oxide Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000004131 Bayer process Methods 0.000 description 1
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910000754 Wrought iron Inorganic materials 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 238000007780 powder milling Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
- C25C3/08—Cell construction, e.g. bottoms, walls, cathodes
- C25C3/12—Anodes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Electrolytic Production Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The present invention relates to a kind of aluminum cell waste cathode carbon block comprehensive recovering process, belong to solid waste technical field of resource comprehensive utilization.The present invention crushes aluminum cell waste cathode carbon block, obtains standby particle；200 400 DEG C are heated to, flotation is carried out after insulation；Obtain breeze, electrolyte slag；Gained electrolyte slag is heated to 550 800 DEG C, insulation, obtains electrolyte powder；Gained breeze is added in alkali lye and leached, and is filtered after leaching, is obtained filter residue and filtrate；Gained filtrate is heated to 60 90 DEG C of temperature and is evaporated crystallization, separates out solid A, filtering, obtains solid A and residual solution；Aluminium hydroxide crystal seed is added into residual solution, and is heated to 25 60 DEG C, is incubated, filtering, obtains solid B and tail washings.Present invention process is reasonable in design, and treatment effeciency is high, each substance recovery and cyclic utilization rate are high, secondary pollution is not produced, suitable for heavy industrialization application.
Description
Technical field
The present invention relates to a kind of aluminum cell waste cathode carbon block comprehensive recovering process, belongs to solid waste comprehensive utilization of resources skill
Art field.
Technical background
Since two thousand one, Chinese Aluminium production capacity ranks first in the world for years, and primary aluminum yield in 2015 is about
31410000 t.Current aluminium electroloysis uses Hall-Ai Lu techniques, because of the infiltration of electrolyte, high temperature aluminium liquid and metal in production process
Erosion of the materials such as sodium to trench bottom, cause aluminium cell run 3~6 years after, it is necessary to stop groove more changeable liner.Research shows, often
1t electrolytic aluminiums are produced, about 10kg waste cathode material can be produced.Calculated with this, China's waste and old cathode material only caused by 2015
Expect just up to 300,000 more than t.
In aluminum electrolysis waste cathode carbon block, charcoal accounts for 30%~70%, and remaining is electrolyte, mainly ice crystal, sodium fluoride,
Calcirm-fluoride, cyanide etc., there is solubility, pernicious gas can be produced by meeting water, can also polluted surface water and underground water.As danger
Solid waste is stored up or landfill, can not only be inherently eliminated the toxicity and corrosivity danger of aluminum electrolysis waste cathode material
Evil, and cause the wasting of resources.Aluminum cell waste cathode material is a kind of available resources rich in charcoal and electrolyte.With
The continuous improvement of the continuous reduction and environmental protection requirement of mineral resources, the comprehensive utilization of aluminum cell waste cathode have turned into
Inexorable trend.
Innovation primary aluminum clearer production technology and application technology as the second resource are improved, handles aluminium electricity efficient and rational, environmental protection and economy
Groove waste lining is solved, is industry problems of the pendulum in face of each metallurgy of aluminium practitioner.For current aluminum cell waste cathode
The problems such as carbon block environmental protection pressure is big, serious waste of resources, expert scholar and production line personnel have carried out many-sided exploration
Research.
Patent CN101357367A provides a kind of method using gangue process aluminum electrolytic groove waste lining, passes through：Raw material
It is broken, levigate, it is the gangue of waste lining quality 10%~30% and the quick lime of waste lining quality 5%~35% by addition
It is well mixed with waste lining；Under the conditions of temperature is 900 DEG C~1200 DEG C, 40min~70min is calcined, calcining matter is levigate to grain
Degree is less than 0.074mm, leaches remaining solvable fluorine ion with the limewash that concentration is 0.5%~5%, extraction time for 30~
60min, filtered afterwards, filtrate uses it for anything else after collecting, and filter residue recovery is available thing.
The A of patent CN 102161049 disclose a kind of method of comprehensive utilization of aluminum cell waste cathode carbon block, its feature
It is：Sorting, broken, milling, ash disposal and dried waste and old cathode carbon block will be passed through as carbon block for blast furnace, electric furnace carbon block, electrolysis
Groove cathode carbon pieces, electrolytic cell side wall carbon block, electrolysis carbon block, self-calcining charcoal blocks or carbon paste production are used with raw material.
Patent CN102992298A discloses a kind of recoverying and utilizing method of electrolytic cell overhaul slag waste cathode carbon block, and it is special
Sign is, electrolytic cell overhaul slag is sorted, and obtains waste cathode carbon block；Water-filling is entered respectively to the cathode carbon pieces block of sorting
Leaching, broken again, water logging after block is selected, the block selected is reclaimed, and remaining powder milling, flotation, is selected therein
Carbon dust.
Patent CN1320491A discloses a kind of comprehensive recovering process of aluminium cell waste liner：By aluminium cell waste liner
Acidolysis is carried out in the acid hydrolysis tank of input injection water and the concentrated sulfuric acid after crushing, caused gas is eluted repeatedly with water, reclaims hydrofluoric acid；
Graphite powder and industrial aluminium hydroxide, aluminum oxide can be produced by producing filter residue and filtrate, its filter residue through filtering after acidolysis in acid hydrolysis tank；Its
Filtrate can produce a variety of fluoride salts, sulfate product.
Patent CN10130268A discloses a kind of method of comprehensive utilization of aluminum cell waste cathode carbon block, mainly will
It is applied to negative and positive the two poles of the earth conduction and exothermic material in the roasting of aluminium cell electric heating, belongs to calcination and is led with material technology
Domain.Application process：1. by aluminum cell waste cathode carbon block coarse crushing, separation wherein rod iron, refractory material, electrolyte etc.；2. will
Crushed by the waste and old cathode carbon block of separation, turn into 1-5mm grain particles；3. broken using the waste and old cathode of different conductances
Particle is laid in aluminium cell, the CURRENT DISTRIBUTION after adjustment energization；4. waste and old cathode particle is by aoxidizing or dragging for breeze mode
Eliminate.
Patent CN101386017A discloses a kind of method for the treatment of aluminum electrolysis waste cathode carbon block using acid and alkali combination method, including
Following steps:(1) aluminum electrolysis waste cathode is added in concentrated alkali solution and reacted, being filtrated to get filtering solid phase, to be added to concentrated acid molten
Reacted in liquid, be filtrated to get carbon dust；(2) filtrate is mixed and instills concentrated alkali solution, regulation pH value is 9, stands filtering, obtains ice
Spar；(3) bleaching powder saturated solution is added in filtrate, filtering is stood, obtains calcirm-fluoride；(4) by four filtrate heating evaporations
Crystallization, obtains solid sodium chloride.
The current recovery processing technique about aluminum electrolysis waste cathode carbon block is more, mostly because complex process, equipment are rotten
The reasons such as erosion is serious, valuable material can not be reclaimed effectively, processing cost height fail to obtain extensive industrial applications.
The content of the invention
At a kind of aluminum cell waste cathode carbon block comprehensive resource recovery
Reason method.
A kind of aluminum cell waste cathode carbon block comprehensive resource recovery and treatment method of the present invention, comprises the steps：
Step 1
Aluminum cell waste cathode carbon block is crushed, obtains standby particle；
Step 2
Standby particle obtained by step 1 is heated to 200-400 DEG C, flotation is carried out after insulation；Obtain breeze, electrolyte slag；
Step 3
Electrolyte slag obtained by step 2 is heated to 550-800 DEG C, insulation, obtains electrolyte powder；
Step 4
Breeze obtained by step 2 is added in alkali lye and leached, is filtered after leaching, obtains filter residue powdered carbon and filtrate；
Step 5
Filtrate obtained by step 4 is heated to 60-90 DEG C of temperature and is evaporated crystallization, solid A is separated out in liquid, filtering, obtains
To solid A and residual solution；
Step 6
Aluminium hydroxide crystal seed is added into residual solution obtained by step 5, and is heated to 25-60 DEG C, is incubated, filtering, consolidate
Body B and tail washings.
A kind of aluminum cell waste cathode carbon block comprehensive resource recovery and treatment method of the present invention, it is described standby in step 1
With in particle, particle diameter accounts for the 60%-90% of standby particle gross mass less than the particle of 200 mesh.
A kind of aluminum cell waste cathode carbon block comprehensive resource recovery and treatment method of the present invention, will be standby obtained by step 1
Particle is heated to 200-400 DEG C, is incubated 10-90min.
A kind of aluminum cell waste cathode carbon block comprehensive resource recovery and treatment method of the present invention, will be standby obtained by step 1
Particle is heated to 200-400 DEG C, is sized mixing after insulation, obtains preselecting slurry, and flotation is carried out to pre-selection slurry；Obtain breeze,
Electrolyte slag；In the pre-selection slurry, solid accounts for the 10%-50% of pre-selection slurry gross mass.
A kind of aluminum cell waste cathode carbon block comprehensive resource recovery and treatment method of the present invention, it is described to preselect in slurry also
Contain collecting agent, foaming agent, inhibitor；The collecting agent is kerosene and/or diesel oil；The foaming agent is No. 2 oil；The suppression
Agent is waterglass.
A kind of aluminum cell waste cathode carbon block comprehensive resource recovery and treatment method of the present invention, the collecting agent is by per ton
The ratio that waste and old cathode carbon block adds 200-600g adds；The foaming agent adds 20-100g's by waste and old cathode carbon block per ton
Ratio adds；The ratio that the inhibitor is added 200-500g in waste and old cathode carbon block per ton adds.
A kind of aluminum cell waste cathode carbon block comprehensive resource recovery and treatment method of the present invention, floatation process are that a step is thick
Choosing.
A kind of aluminum cell waste cathode carbon block comprehensive resource recovery and treatment method of the present invention, separated after flotation breeze,
Electrolyte slag and waste water, waste water recycling.
A kind of aluminum cell waste cathode carbon block comprehensive resource recovery and treatment method of the present invention,
In step 3, electrolyte slag obtained by step 2 is heated to 550-800 DEG C, 30-90min is incubated, obtains electrolyte
Powder；
In step 4, breeze obtained by step 2 is added in alkaline solution and leached, is filtered after leaching, obtains filter residue and filter
Liquid；OH in the alkaline solution—Concentration be 1-5mol/L.
A kind of aluminum cell waste cathode carbon block comprehensive resource recovery and treatment method of the present invention, it is molten that breeze is added into alkalescence
When being leached in liquid, extraction temperature is controlled as 25-100 DEG C, preferably 70-90 DEG C；It is 30-180min to control extraction time；Control
The solid mass ratio of liquid is 5-10:1；Control stir speed (S.S.) 400-1000r/min；The solute of the alkaline solution be selected from NaOH, KOH,
At least one of LiOH, RbOH.Preferably NaOH.
A kind of aluminum cell waste cathode carbon block comprehensive resource recovery and treatment method of the present invention, in step 5, by step
Four gained filtrates are heated to 60-90 DEG C of temperature and are evaporated crystallization 30-180min, separate out solid A in liquid, filter, consolidate
Body A and residual solution；The solid A is sodium salt.
A kind of aluminum cell waste cathode carbon block comprehensive resource recovery and treatment method of the present invention, in step 6, toward remaining
Aluminium hydroxide crystal seed is added in liquid, and is heated to 25-60 DEG C, 30-180min is incubated, filtering, obtains solid B and tail washings；It is described
Solid B is aluminium hydroxide powder；The tail washings reuse；The crystal seed coefficient of the crystal seed is 1~5.
A kind of aluminum cell waste cathode carbon block comprehensive resource recovery and treatment method of the present invention, tail washings need not be handled i.e.
The dipped journey of alkali is can return to reuse
The invention has the advantages that：
1. cyanogen can not only be removed, also favorably by carrying out Low Temperature Heat Treatment to aluminum cell waste cathode carbon block before flotation
Flotation.
2. flotation handles the consumption for by charcoal and electrolyte initial gross separation, reducing the dipped journey alkali of alkali, when shortening alkali leaching
Between.
3. step 3 and step 4 process are simple, operation is convenient, low in raw material price, obtained powdered carbon and electrolyte
Powder purity is high, good in economic efficiency.
4. the filtrate after crystallization precipitation NaF can add decomposing crystal seed of aluminum hydroxide, Bayer process aluminum oxide can also be used as to give birth to
Mother liquor is produced, byproduct for treatment thinking is wide.
In a word, the present invention is under the synergy of each technique.Realize the high efficiente callback of various materials.
Brief description of the drawings
Fig. 1 is present invention process flow chart.
Embodiment
It is described further with reference to specific embodiment, but the present invention is not therefore subject to any restriction.
Embodiment 1
The country certain factory aluminum cell waste cathode carbon block 10g is taken, essential element content is (wt%)：C70.9、Al8.23、
O9.55, F5.38, Na2.57, Fe1.21, crushing and grinding to -200 mesh account for 90%, are laid in 9cm × 6cm flat square porcelain
In boat.
The porcelain boat for filling waste and old cathode powder is put in Muffle furnace, 30min is incubated after being heated to 400 DEG C；Except cyanogen
Waste and old cathode powder is made into ore pulp by mass concentration 25% and water, and roughing is carried out by single-trough flotating machine.Depressing agent is water
Glass, dosage 320g/t waste and old cathodes；Collecting agent is kerosene, dosage 400g/t waste and old cathodes；Foaming agent is No. 2 oil, dosage
40g/t waste and old cathodes.Drying is weighed after flotation froth and underflow are cleaned with water, and it is respectively 7.35g to obtain breeze and electrolyte slag
And 2.46g.
Electrolyte slag is laid in 9cm × 6cm flat square porcelain boat, is placed in Muffle furnace after being heated to 650 DEG C
90min is incubated, obtains the electrolyte powder of 2.454g purity 96.43%.
By liquid-solid ratio 7:1 adds breeze in NaOH concentration 3mol/L aqueous slkali, and the dipped journey of alkali is incubated by water-bath,
100 DEG C, mixing speed 700rpm, reaction time 120min of constant temperature, powdered carbon and filtrate are filtrated to get, it is pure to obtain 6.43g after drying
The powdered carbon of degree 92.87%.
Alkali lixivium evaporative crystallization separates out crystal, and temperature control time 60min, is separated by filtration to obtain crystal at 90 DEG C
0.45g；Filtrate adds aluminium hydroxide powder by crystal seed coefficient 3, and at 40 DEG C, crystallization time 120min, crystallization separates out temperature control
Aluminium hydroxide, separation obtain powder 1.85g after drying, tail washings returns to the dipped journey of alkali and recycled.
Embodiment 2
The country certain factory aluminum cell waste cathode carbon block 30g is taken, essential element content is (wt%)：C70.9、Al8.23、
O9.55, F5.38, Na2.57, Fe1.21, crushing and grinding to -200 mesh account for 80%, are laid in 12cm × 8cm flat square porcelain
In boat.
The porcelain boat for filling waste and old cathode powder is put in Muffle furnace, 10min is incubated after being heated to 400 DEG C；Except cyanogen
Waste and old cathode powder is made into ore pulp by mass concentration 10% and water, and roughing is carried out by single-trough flotating machine.Depressing agent is water
Glass, dosage 200g/t waste and old cathodes；Collecting agent is kerosene, dosage 600g/t waste and old cathodes；Foaming agent is No. 2 oil, dosage
20g/t waste and old cathodes.Drying is weighed after flotation froth and underflow are cleaned with water, and it is respectively 23.64g to obtain breeze and electrolyte slag
And 6.14g.
Electrolyte slag is laid in 9cm × 6cm flat square porcelain boat, is placed in Muffle furnace after being heated to 550 DEG C
60min is incubated, obtains the electrolyte powder of 6.57g purity 95.32%.
By liquid-solid ratio 10:1 adds breeze in NaOH concentration 5mol/L aqueous slkali, and the dipped journey of alkali is protected by water-bath
Temperature, 90 DEG C, mixing speed 1000rpm, reaction time 180min of constant temperature, powdered carbon and filtrate are filtrated to get, are obtained after drying
The powdered carbon of 18.04g purity 92.11%.
Alkali lixivium evaporative crystallization separates out crystal, and temperature control time 30min, is separated by filtration to obtain crystal at 80 DEG C
1.04g；Filtrate adds aluminium hydroxide powder by crystal seed coefficient 3, and at 25 DEG C, crystallization time 120min, crystallization separates out temperature control
Aluminium hydroxide, separation obtain powder 5.28g after drying, tail washings returns to the dipped journey of alkali and recycled.
Embodiment 3
The country certain factory aluminum cell waste cathode carbon block 100g is taken, essential element content is (wt%)：C70.9、Al8.23、
O9.55, F5.38, Na2.57, Fe1.21, broken powder account for 60% to -200 mesh, are laid in 12cm × 8cm flat square porcelain
In boat.
The porcelain boat for filling waste and old cathode powder is put in Muffle furnace, 60min is incubated after being heated to 300 DEG C；Except cyanogen
Waste and old cathode powder is made into ore pulp by mass concentration 30% and water, and roughing is carried out by single-trough flotating machine.Depressing agent is water
Glass, dosage 320g/t waste and old cathodes；Collecting agent is kerosene, dosage 200g/t waste and old cathodes；Foaming agent is No. 2 oil, dosage
100g/t waste and old cathodes.Drying is weighed after flotation froth and underflow are cleaned with water, obtains breeze and electrolyte slag is respectively
80.51g and 22.68g.
Electrolyte slag is laid in 12cm × 8cm flat square porcelain boat, is placed in Muffle furnace after being heated to 800 DEG C
30min is incubated, obtains the electrolyte powder of 19.45g purity 95.82%.
By liquid-solid ratio 7:1 adds breeze in NaOH concentration 1mol/L aqueous slkali, and the dipped journey of alkali is incubated by water-bath,
100 DEG C, mixing speed 600rpm, reaction time 30min of constant temperature, powdered carbon and filtrate are filtrated to get, it is pure to obtain 62.41g after drying
The powdered carbon of degree 92.36%.
Alkali lixivium evaporative crystallization separates out crystal, and temperature control time 180min, is separated by filtration to obtain crystal at 90 DEG C
5.62g；Filtrate adds aluminium hydroxide powder by crystal seed coefficient 1, and at 40 DEG C, crystallization time 180min, crystallization separates out temperature control
Aluminium hydroxide, separation obtain powder 19.44g after drying, tail washings returns to the dipped journey of alkali and recycled.
Embodiment 4
The country certain factory aluminum cell waste cathode carbon block 10g is taken, essential element content is (wt%)：C48.86、
Al14.02, O16.97, F10.08, Na4.58, Fe1.82, broken powder account for 90% to -200 mesh, are laid in 9cm × 6cm's
In flat square porcelain boat.
The porcelain boat for filling waste and old cathode powder is put in Muffle furnace, 60min is incubated after being heated to 200 DEG C；Except cyanogen
Waste and old cathode powder is made into ore pulp by mass concentration 35% and water, and roughing is carried out by single-trough flotating machine.Depressing agent is water
Glass, dosage 500g/t waste and old cathodes；Collecting agent is kerosene, dosage 400g/t waste and old cathodes；Foaming agent is No. 2 oil, dosage
20g/t waste and old cathodes.Drying is weighed after flotation froth and underflow are cleaned with water, and it is respectively 5.27g to obtain breeze and electrolyte slag
And 4.19g.
Electrolyte slag is laid in 9cm × 6cm flat square porcelain boat, is placed in Muffle furnace after being heated to 650 DEG C
90min is incubated, obtains the electrolyte powder of 4.08g purity 95.86%.
By liquid-solid ratio 5:1 adds breeze in NaOH concentration 2mol/L aqueous slkali, and the dipped journey of alkali is incubated by water-bath,
90 DEG C, mixing speed 700rpm, reaction time 120min of constant temperature, powdered carbon and filtrate are filtrated to get, 5.21g purity is obtained after drying
92.48% powdered carbon.
Alkali lixivium evaporative crystallization separates out crystal, and temperature control time 150min, is separated by filtration to obtain crystal at 60 DEG C
0.63g；Filtrate adds aluminium hydroxide powder by crystal seed coefficient 3, and for temperature control at 60 DEG C, crystallization time 30min, crystallization separates out hydrogen
Aluminum oxide, separation obtain powder 2.31g after drying, tail washings returns to the dipped journey of alkali and recycled.
Embodiment 5
The country certain factory aluminum cell waste cathode carbon block 30g is taken, essential element content is (wt%)：C48.86、
Al14.02, O16.97, F10.08, Na4.58, Fe1.82, broken powder account for 90% to -200 mesh, are laid in 12cm × 8cm's
In flat square porcelain boat.
The porcelain boat for filling waste and old cathode powder is put in Muffle furnace, 90min is incubated after being heated to 400 DEG C；Except cyanogen
Waste and old cathode powder is made into ore pulp by mass concentration 25% and water, and roughing is carried out by single-trough flotating machine.Depressing agent is water
Glass, dosage 320g/t waste and old cathodes；Collecting agent is kerosene, dosage 400g/t waste and old cathodes；Foaming agent is No. 2 oil, dosage
40g/t waste and old cathodes.Drying is weighed after flotation froth and underflow are cleaned with water, and it is respectively 16.55g to obtain breeze and electrolyte slag
And 12.18g.
Electrolyte slag is laid in 9cm × 6cm flat square porcelain boat, is placed in Muffle furnace after being heated to 700 DEG C
30min is incubated, obtains the electrolyte powder of 10.47g purity 95.40%.
By liquid-solid ratio 10:1 adds breeze in NaOH concentration 3mol/L aqueous slkali, and the dipped journey of alkali is protected by water-bath
Temperature, 90 DEG C, mixing speed 700rpm, reaction time 120min of constant temperature, powdered carbon and filtrate are filtrated to get, 15.63g is obtained after drying
The powdered carbon of purity 92.52%.
Alkali lixivium evaporative crystallization separates out crystal, and temperature control time 100min, is separated by filtration to obtain crystal at 80 DEG C
1.54g；Filtrate adds aluminium hydroxide powder by crystal seed coefficient 5, and for temperature control at 40 DEG C, crystallization time 90min, crystallization separates out hydrogen
Aluminum oxide, separation obtain powder 7.43g after drying, tail washings returns to the dipped journey of alkali and recycled.
Embodiment 6
The country certain factory aluminum cell waste cathode carbon block 100g is taken, essential element content is (wt%)：C48.86、
Al14.02, O16.97, F10.08, Na4.58, Fe1.82, broken powder account for 90% to -200 mesh, are laid in 12cm × 8cm's
In flat square porcelain boat.
The porcelain boat for filling waste and old cathode powder is put in Muffle furnace, 90min is incubated after being heated to 300 DEG C；Except cyanogen
Waste and old cathode powder is made into ore pulp by mass concentration 50% and water, and roughing is carried out by single-trough flotating machine.Depressing agent is water
Glass, dosage 400g/t waste and old cathodes；Collecting agent is kerosene, dosage 600g/t waste and old cathodes；Foaming agent is No. 2 oil, dosage
100g/t waste and old cathodes.Drying is weighed after flotation froth and underflow are cleaned with water, obtains breeze and electrolyte slag is respectively
58.45g and 36.59g.
Electrolyte slag is laid in 12cm × 8cm flat square porcelain boat, is placed in Muffle furnace after being heated to 650 DEG C
60min is incubated, obtains the electrolyte powder of 39.74g purity 95.67%.
By liquid-solid ratio 7:1 adds breeze in NaOH concentration 3mol/L aqueous slkali, and the dipped journey of alkali is incubated by water-bath,
50 DEG C, mixing speed 400rpm, reaction time 100min of constant temperature, powdered carbon and filtrate are filtrated to get, it is pure to obtain 48.74g after drying
The powdered carbon of degree 92.36%.
Alkali lixivium evaporative crystallization separates out crystal, and temperature control time 60min, is separated by filtration to obtain crystal at 90 DEG C
7.37g；Filtrate adds aluminium hydroxide powder by crystal seed coefficient 4, and at 50 DEG C, crystallization time 120min, crystallization separates out temperature control
Aluminium hydroxide, separation obtain powder 25.42g after drying, tail washings returns to the dipped journey of alkali and recycled.
Claims (10)
1. a kind of aluminum cell waste cathode carbon block comprehensive recovering process, it is characterised in that comprise the steps：
Step 1
Aluminum cell waste cathode carbon block is crushed, obtains standby particle；
Step 2
Standby particle obtained by step 1 is heated to 200-400 DEG C, flotation is carried out after insulation, obtains breeze, electrolyte slag；
Step 3
Electrolyte slag obtained by step 2 is heated to 550-800 DEG C, insulation, obtains electrolyte powder；
Step 4
Breeze obtained by step 2 is added in alkali lye and leached, is filtered after leaching, obtains filter residue and filtrate；
Step 5
Filtrate obtained by step 4 is heated to 60-90 DEG C of temperature and is evaporated crystallization, solid A is separated out in liquid, filters, consolidate
Body A and residual solution；
Step 6
Add aluminium hydroxide crystal seed into residual solution obtained by step 5, be heated to 25-60 DEG C, be incubated, filtering, obtain solid B and
Tail washings.
A kind of 2. aluminum cell waste cathode carbon block comprehensive recovering process according to claim 1, it is characterised in that：Step
In one, in the standby particle, particle diameter accounts for the 60%-90% of standby particle gross mass less than the particle of 200 mesh.
A kind of 3. aluminum cell waste cathode carbon block comprehensive recovering process according to claim 1, it is characterised in that：Will step
The standby particle of a rapid gained is heated to 200-400 DEG C, is incubated 10-90min.
A kind of 4. aluminum cell waste cathode carbon block comprehensive recovering process according to claim 1, it is characterised in that：Will step
The standby particle of a rapid gained is heated to 200-400 DEG C, is sized mixing after insulation, obtains preselecting slurry, and pre-selection slurry is floated
Choosing；Obtain breeze, electrolyte slag；In the pre-selection slurry, solid accounts for the 10%-50% of pre-selection slurry gross mass.
A kind of 5. aluminum cell waste cathode carbon block comprehensive recovering process according to claim 4, it is characterised in that：It is described
Preselect in slurry also containing collecting agent, foaming agent, inhibitor；The collecting agent is kerosene and/or diesel oil；The foaming agent is 2
Number oil；The inhibitor is waterglass.
A kind of 6. aluminum cell waste cathode carbon block comprehensive recovering process according to claim 5, it is characterised in that：It is described
The ratio that collecting agent is added 200-600g in waste and old cathode carbon block per ton adds；The foaming agent is added by waste and old cathode carbon block per ton
The ratio for entering 20-100g adds；The ratio that the inhibitor is added 200-500g in waste and old cathode carbon block per ton adds.
A kind of 7. aluminum cell waste cathode carbon block comprehensive recovering process according to claim 1, it is characterised in that：
In step 3, electrolyte slag obtained by step 2 is heated to 550-800 DEG C, 30-90min is incubated, obtains electrolyte powder；
In step 4, breeze obtained by step 2 is added in alkali lye and leached, is filtered after leaching, obtains filter residue and filtrate；The alkali
OH in liquid—Concentration be 1-5mol/L.
A kind of 8. aluminum cell waste cathode carbon block comprehensive recovering process according to claim 7, it is characterised in that：By charcoal
When being leached in slag addition alkali lye, it is 25-100 DEG C to control extraction temperature；It is 30-180min to control extraction time；Control liquid stereoplasm
It is 5-10 to measure ratio:1；Control-the 1000r/min of stir speed (S.S.) 400；The solute of the alkali lye is selected from NaOH, KOH, LiOH, RbOH
At least one of.
A kind of 9. aluminum cell waste cathode carbon block comprehensive recovering process according to claim 1, it is characterised in that：Step
In five, filtrate obtained by step 4 is heated to 60-90 DEG C of temperature and is evaporated crystallization 30-180min, solid A is separated out in liquid,
Filtering, obtains solid A and residual solution；The solid A is sodium salt.
A kind of 10. aluminum cell waste cathode carbon block comprehensive recovering process according to claim 1, it is characterised in that：Step
In rapid six, aluminium hydroxide crystal seed is added into residual solution, and is heated to 25-60 DEG C, 30-180min is incubated, filtering, obtains solid
B and tail washings；The solid B is aluminium hydroxide powder；The tail washings reuse；The crystal seed coefficient of the aluminium hydroxide crystal seed is 1 ~ 5.
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| CN107662913B (en) * | 2017-09-30 | 2020-05-12 | 山东绿脉铝业科技有限公司 | Processing method of aluminum electrolysis waste cathode carbon block |
| CN109399605A (en) * | 2018-12-09 | 2019-03-01 | 湖南涌鑫源环保有限公司 | A kind of system of discarded cathode carbon pieces environmental protection treatment |
| CN109437150A (en) * | 2018-12-09 | 2019-03-08 | 湖南涌鑫源环保有限公司 | The processing of cathode carbon pieces, carbon slag environmental protection that cell body is discarded utilizes method |
| CN109719118A (en) * | 2019-01-04 | 2019-05-07 | 亚太环保股份有限公司 | A kind of aluminium cell solid waste recycling treatment system and method |
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| CN110180862B (en) * | 2019-05-20 | 2021-09-14 | 六盘水师范学院 | Sodium-embedded graphite prepared from aluminum electrolysis waste cathode and application thereof |
| CN110408959B (en) * | 2019-07-25 | 2021-03-26 | 中南大学 | Method for recovering carbon and electrolyte from aluminum electrolysis waste cathode carbon blocks |
| CN110407190B (en) * | 2019-07-25 | 2023-01-06 | 中南大学 | Method for recycling carbon from waste aluminum electrolysis cathode |
| CN111020638A (en) * | 2019-11-06 | 2020-04-17 | 东北大学 | Method for treating anode carbon slag of aluminum electrolysis cell by using sodium carbonate molten salt method |
| CN111233019A (en) * | 2020-04-11 | 2020-06-05 | 兰州理工大学 | Environment-friendly treatment method for waste cathode and aluminum ash of aluminum electrolysis cell |
| CN111777054B (en) * | 2020-07-07 | 2021-02-05 | 昆明理工大学 | Method for removing fluorine by using aluminum electrolysis waste cathode carbon block through microwave-ultrasonic wave-alkaline leaching |
| CN112322076B (en) * | 2020-11-04 | 2021-10-01 | 中南大学 | Method for preparing carbon black |
| CN113426807B (en) * | 2021-06-29 | 2022-05-17 | 云南云铝润鑫铝业有限公司 | Method for combined treatment and comprehensive utilization of resources of dangerous waste residues generated in aluminum electrolysis |
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